Polyether amine modified epoxy curing agent and preparation method thereof

Abstract

The invention discloses a polyether amine modified epoxy curing agent and a preparation method thereof. The polyether amine modified epoxy curing agent is prepared from the following components in percentage by mass: 12.5 to 38 percent of polyether amine, 22 to 37.5 percent of alicyclic amine, 15 to 25 percent of epoxy resin and 15 to 3 percent of aromatic alcohol. Performance detection shows that the cured product has the characteristics of quick drying and high hardness, also has good toughness and impact resistance, is colorless under a normal-temperature curing condition, can be used for surface coating, has good curing performance and excellent weather resistance, and is mainly suitable for epoxy floor coatings, building structural adhesives and the like.

Description

Technical Field

[0001] The invention relates to a polyetheramine modified epoxy curing agent, belonging to the technical field of polymer materials. Background Art

[0002] The two-component system composed of epoxy resin and epoxy resin curing agent is widely used in floor coatings, anti-corrosion coatings, adhesives, composite materials and other fields due to its small curing shrinkage, adhesion, heat resistance, chemical resistance, and excellent mechanical and electrical properties.

[0003] As human society pays more and more attention to environmental protection, primary polyethylene polyamine and aromatic amine curing agents have been replaced by non-toxic or low-toxic modified amines. Conventional epoxy resin curing generally has poor weather resistance, which is often difficult to achieve with ordinary curing agents. Some accelerators need to be added to achieve the effect. However, if too much accelerator is added, the epoxy resin curing material will become brittle and have poor performance, which cannot meet the application requirements. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide an epoxy curing agent with good construction performance, moderate viscosity, good compatibility with most curing agents and epoxy products, low product toxicity, high gloss of cured film, wide range of epoxy resin ratio, and can adjust the ratio according to different needs according to the needs of application occasions. It is mainly used for anti-corrosion coatings, epoxy fiberglass, concrete mortar, good construction performance agent, epoxy solvent floor coating, adhesive, epoxy dry hanging glue, and potting glue; another purpose of the present invention is to provide a preparation method of the epoxy curing agent.

[0005] Technical solution: To achieve the above purpose, the technical solution adopted by the present invention is:

[0006] A polyetheramine modified epoxy curing agent is prepared from the following raw materials in percentage by mass:

[0007] It is made of 12.5%-38% polyetheramine, 22-37.5% alicyclic amine, 15-25% epoxy resin E51, and 15%-233% aromatic alcohols.

[0008] As a preferred solution, the polyetheramine modified epoxy curing agent described above, the polyetheramine can be selected from Zibo Zhengda ZD-123.

[0009] As a preferred embodiment, in the above-mentioned polyetheramine modified epoxy curing agent, the alicyclic type can be selected from isophorone diamine (IPDA).

[0010] As a preferred embodiment, the epoxy curing agent modified by polyetheramine mentioned above, the epoxy resin is epoxy resin E51.

[0011] As a preferred embodiment, in the above-mentioned polyetheramine modified epoxy curing agent, the aromatic alcohol is benzyl alcohol.

[0012] The present invention provides a method for preparing a polyetheramine modified epoxy curing agent, which comprises the following steps:

[0013] (1) adding polyetheramine and alicyclic amine into a reaction kettle according to mass percentage, and stirring to make the materials uniformly mixed;

[0014] (2) Then, nitrogen or carbon dioxide protective gas is introduced to remove the air in the kettle, and the temperature is raised to 50-60°C;

[0015] (3) Pour the measured epoxy resin into the high-level tank;

[0016] (4) Add aromatic alcohol into the high-level tank and start stirring to make the materials evenly stirred;

[0017] (5) adding a mixture of epoxy resin and aromatic alcohol dropwise for at least 1 hour, with the temperature controlled at 60-70°C;

[0018] (6) After the addition is complete, control the temperature at 60-70°C and keep the reaction for 1-3 hours;

[0019] (7) After the insulation is completed, the central control measures the amine value and viscosity to obtain the polyetheramine modified epoxy curing agent.

[0020] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0021] The present invention obtains the best raw material ratio composition through a large number of experimental screenings. According to the performance requirements of the application occasions, the present invention has good flexibility of the cured product due to the long class segment of the polyetheramine, and good weather resistance due to the addition of alicyclic amine.

[0022] The present invention found in the experimental process that the amount of each raw material is very critical. When the polyetheramine is more than the amount of the present invention, the curing speed will be slow; when the amount of the alicyclic amine is less than the amount of the present invention, the hardness of the cured product will be poor. Therefore, the present invention screened through a large number of experiments to obtain the best composition and amount ratio of each raw material.

[0023] After performance testing, the results show that the epoxy curing agent prepared by the invention has excellent performance indicators such as hardness and flexibility. In addition, under room temperature curing conditions, it has good curing performance and excellent weather resistance. It can meet the application requirements of floor intermediate coating, top coating and building structural adhesive, and has achieved very good technical results. DETAILED DESCRIPTION

[0024] Example 1

[0025] 1. A polyetheramine modified epoxy curing agent, which is made of the following raw materials in percentage by mass:

[0026] 12.5% ​​polyetheramine (ZD-123 provided by Zibo Zhengda), 37.5% isofluorodione diamine, 20% epoxy resin E51, and 30% benzyl alcohol.

[0027] 2. A method for preparing a polyetheramine modified epoxy curing agent, comprising the following steps:

[0028] (1) adding polyetheramine and isophorone diamine into a reaction kettle according to mass percentage, and stirring to make the materials uniformly mixed;

[0029] (2) Then, nitrogen protective gas is introduced to remove the air in the kettle, and the temperature is raised to 50-60°C;

[0030] (3) Pour the measured epoxy resin E51 into the high-level tank;

[0031] (4) putting benzyl alcohol into a high-level tank and starting stirring to make the materials evenly stirred;

[0032] (5) adding a mixture of epoxy resin E51 and benzyl alcohol dropwise for at least 1 hour, with the temperature controlled at 60-70°C;

[0033] (6) After the addition is complete, control the temperature at 60-70°C and keep the reaction for 2 hours;

[0034] (7) After the insulation is completed, the central control measures the amine value to be 280-320 mgKOH / g (hydrochloric acid-ethanol method) and the viscosity to be 400-600 mPa.S / 25°C, and the polyetheramine modified epoxy curing agent is obtained.

[0035] Example 2

[0036] 1. A polyetheramine-modified epoxy curing agent, which is made of the following raw materials in percentage by mass:

[0037] Polyetheramine 20% (ZD-123 provided by Zibo Zhengda), 32% isofluorodione diamine (IPDA),

[0038] 15% epoxy resin E51, 33% benzyl alcohol.

[0039] 2. A method for preparing a polyetheramine modified epoxy curing agent, comprising the following steps:

[0040] (1) adding polyetheramine and isophorone diamine (IPDA) into a reaction kettle according to mass percentage, and stirring to make the materials uniformly mixed;

[0041] (2) Then, carbon dioxide protective gas is introduced to remove the air in the kettle, and the temperature is raised to 50-60°C;

[0042] (3) Pour the measured epoxy resin E51 into the high-level tank;

[0043] (4) putting benzyl alcohol into a high-level tank and starting stirring to make the materials evenly stirred;

[0044] (5) adding a mixture of epoxy resin E51 and benzyl alcohol dropwise for at least 1 hour, with the temperature controlled at 60-70°C;

[0045] (6) After the addition is complete, control the temperature at 60-70°C and keep the reaction for 2 hours;

[0046] (7) After the insulation is completed, the central control measures the amine value to be 300-340 mgKOH / g (hydrochloric acid-ethanol method) and the viscosity to be 1500-2500 mPa.S / 25°C, and obtains the polyetheramine modified epoxy curing agent.

[0047] Example 3

[0048] 1. A polyetheramine-modified epoxy curing agent, which is made of the following raw materials in percentage by mass:

[0049] 38% polyetheramine (ZD-123 provided by Zibo Zhengda), 22% isofluorodione diamine (IPDA), 25% epoxy resin E51, and 15% benzyl alcohol.

[0050] 2. A method for preparing a polyetheramine modified epoxy curing agent, comprising the following steps:

[0051] (1) adding polyetheramine and isofluorodione diamine (IPDA) into a reaction kettle according to mass percentage, and stirring to mix the materials evenly;

[0052] (2) Then, carbon dioxide protective gas is introduced to remove the air in the kettle, and the temperature is raised to 50-60°C;

[0053] (3) Pour the measured epoxy resin E51 into the high-level tank;

[0054] (4) putting benzyl alcohol into a high-level tank and starting stirring to make the materials evenly stirred;

[0055] (5) adding a mixture of epoxy resin E51 and benzyl alcohol dropwise for at least 1 hour, with the temperature controlled at 60-70°C;

[0056] (6) After the addition is complete, control the temperature at 60-70°C and keep the reaction for 2 hours;

[0057] (7) After the insulation is completed, the central control measures the amine value to be 290-330 mgKOH / g (hydrochloric acid-ethanol method) and the viscosity to be 150-400 mPa.S / 25°C, and obtains a polyetheramine modified epoxy curing agent.

[0058] Example 4 Performance Test

[0059] According to Table 1 below, epoxy resin (epoxy resin 828 produced by Jiangsu Sanmu Chemical Co., Ltd.), diluent, filler, auxiliary agent and polyetheramine modified epoxy curing agent prepared in Examples 1 to 3 were mixed in proportion to make epoxy floor topcoat and evenly coated on epoxy floor midcoat. The basic properties measured after curing are shown in Table 2 below.

[0060] Table 1: Experimental recipe

[0061] .

[0063] Table 2: Performance test results of polyetheramine modified curing agent examples with different formulation ratios

[0064]

[0065]

[0066] After comprehensive analysis of the three embodiments, the curing performance of embodiment 2 is the best.

[0067] Table 3 Paint film weather resistance test

[0068] Test items Example 1 Example 2 Example 3 Detection Methods Powdering degree and grade Level 1 Level 0 Level 1 GB / T1766-2008 The degree of gloss change of paint film aging Slight loss of gloss No light loss Light time GB / T9574 Light loss rate 4－15 ≤3 4－15 GB / T9574 Color change level Level 1 Level 0 Level 1 GB / T1186 Color difference value / E* 1.6-3.0 ≤1.5 1.6-3.0 GB / T1186 .

[0069] The above performance test results show that the modified epoxy curing agent prepared by the present invention using different raw materials through a large number of experimental screenings has excellent performance indicators such as appearance, hardness, flexibility, etc., and a moderate curing time, which meets the application requirements of most customers and achieves very good technical effects. Comprehensive analysis shows that the paint film of Example 2 has the best weather resistance.

[0070] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A polyetheramine modified epoxy curing agent, characterized in that: It is made of the following raw materials in percentage by mass: 12.5%-38% polyetheramine, 22-37.5% alicyclic amines, 15-25% epoxy resin, 15%-33% aromatic alcohols.

2. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: It is made of the following raw materials in percentage by mass: 12.5% ​​polyetheramine, 37.5% isofluorodione diamine, 20% epoxy resin, 30% aromatic alcohol.

3. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: It is made of the following raw materials in percentage by mass: 20% polyetheramine, 32% isofluorodione diamine, 15% epoxy resin E51, 33% aromatic alcohols.

4. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: It is made of the following raw materials in percentage by mass: 20% polyetheramine, 32% isofluorodione diamine, 15% epoxy resin E51, 33% aromatic alcohols.

5. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: The alicyclic amine used was isophorone diamine.

6. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: The epoxy resin used was epoxy resin E51.

7. The polyetheramine modified epoxy curing agent according to claim 1, characterized in that: The aromatic alcohol used was benzyl alcohol.

8. The method for preparing the polyetheramine modified epoxy curing agent according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) adding polyetheramine and alicyclic amine into a reaction kettle according to mass percentage, and stirring to make the materials uniformly mixed; (2) Then, nitrogen or carbon dioxide protective gas is introduced to remove the air in the kettle, and the temperature is raised to 50-60°C; (3) Pour the measured epoxy resin into the high-level tank; (4) Add aromatic alcohol into the high-level tank and start stirring to make the materials evenly stirred; (5) adding a mixture of epoxy resin and aromatic alcohol dropwise for at least 1 hour, with the temperature controlled at 60-70°C; (6) After the addition is complete, control the temperature at 60-70°C and keep the reaction for 1-3 hours; (7) After the insulation is completed, the central control measures the amine value and viscosity to obtain the polyetheramine modified epoxy curing agent.

9. Use of the polyetheramine modified epoxy curing agent according to any one of claims 1 to 7 as an epoxy resin curing agent.

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